CN116850791B - Reverse osmosis membrane and preparation method thereof - Google Patents
Reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN116850791B CN116850791B CN202311127865.XA CN202311127865A CN116850791B CN 116850791 B CN116850791 B CN 116850791B CN 202311127865 A CN202311127865 A CN 202311127865A CN 116850791 B CN116850791 B CN 116850791B
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- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 43
- 229920002647 polyamide Polymers 0.000 claims abstract description 43
- -1 aromatic acyl chloride Chemical class 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000012071 phase Substances 0.000 claims abstract description 23
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000011265 semifinished product Substances 0.000 claims abstract description 12
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 37
- 235000012141 vanillin Nutrition 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 23
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002262 Schiff base Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229960003237 betaine Drugs 0.000 claims description 8
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 6
- PUOAVIXAHBUMSL-UHFFFAOYSA-N dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O.C[NH+](C)CCOC(=O)C(C)=C PUOAVIXAHBUMSL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a reverse osmosis membrane and a preparation method thereof, which belong to the technical field of reverse osmosis membranes and comprise the following preparation steps: adding hyperbranched polyamide additive and polyamine into deionized water containing surfactant at 20-40 ℃ and stirring for 0.5-1.5h to obtain aqueous phase solution; adding aromatic acyl chloride into organic solvent, stirring at 35-55deg.C for 1-1.5 hr to obtain oil phase solution; soaking a polysulfone support membrane in a water phase solution for 1-5min, taking out, pressing to remove surface liquid, drying in the shade at room temperature to obtain a semi-finished product, pouring an oil phase solution into the surface of the semi-finished product, standing for 10s, pouring the oil phase solution, and obtaining a reverse osmosis membrane after the surface organic solvent is completely volatilized.
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membranes, and particularly relates to a reverse osmosis membrane and a preparation method thereof.
Background
The reverse osmosis membrane belongs to an artificial semipermeable membrane manufactured by imitating biological semipermeable membranes, and the technical principle is that sewage or solution to be treated is controlled to pass through the reverse osmosis membrane at a higher speed, and substances such as organic matters, dissolved salts, microorganisms and the like mixed in the sewage and the solution are intercepted by virtue of the smaller pore diameter of a membrane material, so that the purposes of sewage treatment and solution filtration and purification are realized.
During the operation of a reverse osmosis membrane system, the problem of biological pollution often occurs, the service life of the membrane system is shortened, antibacterial agents such as nano silver, copper ions, zinc ions and the like are used for modifying a membrane material to improve the pollution resistance of the membrane material, for example, a composite reverse osmosis membrane resistant to microbial pollution disclosed in China patent CN101874989B and a preparation method thereof are adopted, a polyamide membrane layer modified by nano inorganic antibacterial particles is formed on the surface of a polysulfone supporting layer on the basis of generating the polyamide membrane layer, the pollution resistance of the membrane material is improved, the thickness of the membrane layer is increased, the pure water flux of the membrane is sacrificed when the pollution resistance of the composite membrane is improved due to the excessively thick membrane layer, and in practical application, the sterilization range is limited only on the periphery of the surface of the membrane material (the antibacterial effect is achieved only when microorganisms are contacted with nano antibacterial particles on the surface of the membrane material), and the biological pollution resistance is limited.
Therefore, providing a reverse osmosis membrane resistant to biological contamination is a technical problem that needs to be solved at present.
Disclosure of Invention
The invention aims to provide a reverse osmosis membrane and a preparation method thereof, which are used for solving the problems in the background technology.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing a reverse osmosis membrane comprising the steps of:
soaking the polysulfone support membrane in the aqueous phase solution for 1-5min, taking out, pressing surface liquid by using a rubber roller, drying in the shade at room temperature to obtain a semi-finished product, pouring the oil phase solution into the surface of the semi-finished product, standing for 10s, pouring the oil phase solution out, and obtaining the reverse osmosis membrane after the surface organic solvent is completely volatilized.
Wherein the aqueous phase solution is prepared by the steps of:
adding the hyperbranched polyamide additive and the polyamine into deionized water containing a surfactant and having the temperature of 20-40 ℃ and stirring for 0.5-1.5h, wherein the mass fraction of the hyperbranched polyamide additive is 1-1.5%, the mass fraction of the polyamine is 2-4%, and the mass fraction of the surfactant is 0.1-0.8%.
The oil phase solution is prepared by the following steps:
adding aromatic acyl chloride into organic solvent, and stirring at 35-55deg.C for 1-1.5 hr.
Further, the hyperbranched polyamide additive is prepared by the following steps:
s1, adding vanillin methyl ester monomer into a reaction kettle, slowly dropwise adding tri (2-aminoethyl) amine, heating to 100 ℃ after the dropwise adding is finished, starting stirring, dropwise adding N, N-dimethylacetamide after 2h of reaction, heating to 120 ℃ after the dropwise adding is finished, heating to 140 ℃ after 2h of reaction, reacting for 6-7h, and washing a reaction product by a mixed solvent consisting of anhydrous diethyl ether and petroleum ether with the volume of 1:1 to obtain amino-terminated hyperbranched polyamide;
and S2, adding the amino-terminated hyperbranched polyamide into methanol, then adding a betaine type amphoteric ion compound containing carbon-carbon double bonds, continuously stirring at room temperature for reaction for 48 hours, and removing the methanol by reduced pressure distillation after the reaction is finished to obtain the hyperbranched polyamide additive.
Further, the ratio of vanillin methyl ester monomer, tris (2-aminoethyl) amine and N, N-dimethylacetamide in step S1 was 1g:0.59-0.67g:4mL, taking vanillin methyl ester monomer and ethylenediamine as monomers, and carrying out amidation reaction to obtain the amino-terminated hyperbranched polyamide.
Further, the dosage of the betaine type amphoteric ion compound containing carbon-carbon double bonds in the step S2 is 2-3% of the mass of the amino-terminated hyperbranched polyamide, and the betaine type amphoteric ion compound is introduced into the amino-terminated hyperbranched polyamide structure through Michael addition reaction, so that the hyperbranched polyamide additive is obtained.
Further, the betaine type amphoteric ion compound containing carbon-carbon double bond is one or more of N, N-dimethyl (methacryloxyethyl) ammonium propane sulfonic acid inner salt, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonic acid inner salt, N-dimethyl-N-acrylamidopropyl-N-propane sulfonic acid inner salt and N, N-dimethyl-N-acrylamidopropyl-N-propane sulfonic acid inner salt.
Further, the preparation steps of the vanillin methyl ester monomer are as follows:
step a, dissolving vanillin in absolute ethyl alcohol, stirring and heating to 70 ℃, dropwise adding an absolute ethyl alcohol solution of p-phenylenediamine, keeping the temperature and stirring for reaction for 2 hours after the dropwise adding is finished, standing, cooling to room temperature, carrying out vacuum filtration, washing a filter cake with absolute ethyl alcohol for 3-4 times, and carrying out vacuum drying to obtain an amino-terminated vanillin Schiff base compound;
wherein, the mol ratio of vanillin to p-phenylenediamine is 1:1, utilizing the Schiff base reaction of the aldehyde group of vanillin and the amino group of p-phenylenediamine to obtain an amino-terminated vanillin Schiff base compound, wherein the molecular structural formula of the amino-terminated vanillin Schiff base compound is shown as follows:
；
step b, adding methanol, an amino-terminated vanillin Schiff base compound and methyl acrylate into a flask, heating to reflux for reaction for 5-7h under the protection of nitrogen, and removing methanol and excessive methyl acrylate by reduced pressure rotary evaporation after the reaction is finished to obtain vanillin methyl ester monomers;
wherein the mass ratio of the amino-terminated vanillin Schiff base compound to the methyl acrylate is 2.6:2.5-3.2, the amino group of the amino-terminated vanillin Schiff base compound and the vinyl double bond of methyl acrylate are subjected to Michael addition reaction to obtainTo vanillin methyl ester monomer, the molecular structure is as follows:。
further, the polyamine is one or more of diethylamine, triethylamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, piperazine, 4-aminomethylpiperazine, m-phenylenediamine, o-phenylenediamine and p-phenylenediamine.
Further, the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium glycocholate, dioctyl sodium succinate, sodium dodecyl sulfate and sodium laurylsulfate.
Further, the aromatic acyl chloride is one or more of trimesoyl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride and phthaloyl chloride.
Further, the organic solvent is n-hexane.
A reverse osmosis membrane is prepared by the preparation method.
The invention has the beneficial effects that:
1. the reverse osmosis membrane and the preparation method thereof provided by the invention are simple and feasible, the obtained reverse osmosis membrane has long-term stable pollution resistance, the structure of the polyamide membrane is optimized, and the membrane flux and the salt rejection rate are improved; under the pressure of 1.55MPa, the raw water concentration (NaCl) is 2mg/mL, the temperature is 25 ℃, the bovine serum albumin is 1mg/mL polluted, and the water flux recovery rate after 12h pollution is more than 96.5 percent.
2. The hyperbranched polyamide additive is introduced into the aqueous phase solution, contains active amino groups, can be polymerized with the oil phase solution to form a highly crosslinked three-dimensional reticular polyamide layer, and ensures the salt interception performance of the reverse osmosis membrane; secondly, the membrane has a highly branched structure and contains a large number of cavity structures, so that additional water channels can be provided to improve the overall water flux of the membrane; furthermore, the molecular interior of the compound contains a vanillin Schiff base structure, the Schiff base group can be combined with anions or sulfhydryl groups of a microbial cell membrane to inhibit the growth and reproduction of microorganisms, and simultaneously, phenolic hydroxyl groups on the vanillin structure have an antibacterial effect; finally, the tail end of the membrane material contains betaine type zwitterionic compound, and the introduction of the zwitterionic compound plays a role in inhibiting bacteria and proteins from adhering to the surface of the reverse osmosis membrane on one hand and plays a role in improving the desalination rate of the membrane material on the other hand; in conclusion, the reverse osmosis membrane prepared by the method has long-term stable pollution resistance and higher interception and separation characteristics.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A vanillin methyl ester monomer is prepared by the following steps:
step a, dissolving 0.1mol of vanillin in 150mL of absolute ethyl alcohol, stirring and heating to 70 ℃, dropwise adding a p-phenylenediamine absolute ethyl alcohol solution consisting of 0.1mol of p-phenylenediamine and 100mL of absolute ethyl alcohol, after the dropwise adding is finished, carrying out heat preservation and stirring reaction for 2 hours, standing, cooling to room temperature, carrying out vacuum filtration, washing a filter cake with absolute ethyl alcohol for 3 times, and carrying out vacuum drying to obtain an amino-terminated vanillin Schiff base compound;
step b, adding 60mL of methanol, 2.6g of amino-terminated vanillin Schiff base compound and 2.5g of methyl acrylate into a flask, heating to reflux under the protection of nitrogen, and removing methanol and excessive methyl acrylate by rotary evaporation under reduced pressure after the reaction is finished to obtain vanillin methyl ester monomer.
Example 2
A vanillin methyl ester monomer is prepared by the following steps:
step a, dissolving 0.1mol of vanillin in 150mL of absolute ethyl alcohol, stirring and heating to 70 ℃, dropwise adding a p-phenylenediamine absolute ethyl alcohol solution consisting of 0.1mol of p-phenylenediamine and 100mL of absolute ethyl alcohol, after the dropwise adding is finished, carrying out heat preservation and stirring reaction for 2 hours, standing, cooling to room temperature, carrying out vacuum filtration, washing a filter cake with absolute ethyl alcohol for 4 times, and carrying out vacuum drying to obtain an amino-terminated vanillin Schiff base compound;
and b, adding 80mL of methanol, 2.6g of amino-terminated vanillin Schiff base compound and 3.2g of methyl acrylate into a flask, heating to reflux under the protection of nitrogen, and removing methanol and excessive methyl acrylate by rotary evaporation under reduced pressure after the reaction is finished to obtain vanillin methyl ester monomer.
Example 3
A hyperbranched polyamide additive is prepared by the following steps:
step S1, adding 1g of vanillin methyl ester monomer of the embodiment 1 into a reaction kettle, slowly dropwise adding 0.59g of tri (2-aminoethyl) amine, heating to 100 ℃ after the dropwise adding is finished, starting stirring, dropwise adding 4mL of N, N-dimethylacetamide after 2h of reaction, heating to 120 ℃ after the dropwise adding is finished, heating to 140 ℃ after 2h of reaction, and reacting for 6h, and washing a reaction product by a mixed solvent consisting of anhydrous diethyl ether and petroleum ether with the volume of 1:1 to obtain amino-terminated hyperbranched polyamide;
s2, adding the amino-terminated hyperbranched polyamide into methanol, then adding N, N-dimethyl (methacryloyloxyethyl) ammonium propane sulfonic acid inner salt, continuously stirring at room temperature for reaction for 48 hours, and removing the methanol by reduced pressure distillation after the reaction is finished to obtain the hyperbranched polyamide additive, wherein the dosage of the N, N-dimethyl (methacryloyloxyethyl) ammonium propane sulfonic acid inner salt is 2% of the mass of the amino-terminated hyperbranched polyamide.
Example 4
A hyperbranched polyamide additive is prepared by the following steps:
step S1, adding 1g of vanillin methyl ester monomer of the embodiment 2 into a reaction kettle, slowly dropwise adding 0.67g of tri (2-aminoethyl) amine, heating to 100 ℃ after the dropwise adding is finished, starting stirring, dropwise adding 4mL of N, N-dimethylacetamide after 2h of reaction, heating to 120 ℃ after the dropwise adding is finished, heating to 140 ℃ after 2h of reaction, reacting for 7h, and washing a reaction product by a mixed solvent consisting of anhydrous diethyl ether and petroleum ether with the volume of 1:1 to obtain amino-terminated hyperbranched polyamide;
s2, adding the amino-terminated hyperbranched polyamide into methanol, then adding N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonic acid inner salt, continuously stirring at room temperature for reacting for 48 hours, and removing the methanol by reduced pressure distillation after the reaction is finished to obtain the hyperbranched polyamide additive, wherein the dosage of the N, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonic acid inner salt is 3% of the mass of the amino-terminated hyperbranched polyamide.
Comparative example 1
This comparative example is the product obtained in step S1 of example 4 (amino terminated hyperbranched polyamide).
Example 5
A method for preparing a reverse osmosis membrane comprising the steps of:
soaking a polysulfone support membrane in a water phase solution for 1min, taking out, pressing surface liquid by using a rubber roller, drying in the shade at room temperature to obtain a semi-finished product, pouring an oil phase solution into the surface of the semi-finished product, standing for 10s, pouring the oil phase solution, and obtaining the reverse osmosis membrane after the surface organic solvent is completely volatilized.
Wherein the aqueous phase solution is prepared by the steps of:
the hyperbranched polyamide additive and the polyamine of the example 3 are added into deionized water containing a surfactant and at the temperature of 23 ℃ and stirred for 0.5h, wherein the mass fraction of the hyperbranched polyamide additive is 1%, the mass fraction of the polyamine is 2%, and the mass fraction of the surfactant is 0.1%.
Wherein the oil phase solution is prepared by the following steps:
adding trimesoyl chloride into n-hexane, and stirring at 35 ℃ for 1.5 h.
The polyamine is prepared from diethylamine and piperazine according to a mass ratio of 1:1, wherein the surfactant is sodium dodecyl benzene sulfonate.
Example 6
A method for preparing a reverse osmosis membrane comprising the steps of:
soaking a polysulfone support membrane in a water phase solution for 1min, taking out, pressing surface liquid by using a rubber roller, drying in the shade at room temperature to obtain a semi-finished product, pouring an oil phase solution into the surface of the semi-finished product, standing for 10s, pouring the oil phase solution, and obtaining the reverse osmosis membrane after the surface organic solvent is completely volatilized.
Wherein the aqueous phase solution is prepared by the steps of:
the hyperbranched polyamide additive and the polyamine of the example 4 are added into deionized water containing a surfactant and at 35 ℃ and stirred for 1h, wherein the mass fraction of the hyperbranched polyamide additive is 1.3%, the mass fraction of the polyamine is 3%, and the mass fraction of the surfactant is 0.5%.
Wherein the oil phase solution is prepared by the following steps:
adding isophthaloyl dichloride into n-hexane, and stirring at 45 ℃ for 1 h.
The polyamine is diethylamine, piperazine and 4-aminomethylpiperazine according to the mass ratio of 1:2:1, wherein the surfactant is sodium dodecyl benzene sulfonate.
Example 7
A method for preparing a reverse osmosis membrane comprising the steps of:
soaking a polysulfone support membrane in a water phase solution for 1min, taking out, pressing surface liquid by using a rubber roller, drying in the shade at room temperature to obtain a semi-finished product, pouring an oil phase solution into the surface of the semi-finished product, standing for 10s, pouring the oil phase solution, and obtaining the reverse osmosis membrane after the surface organic solvent is completely volatilized.
Wherein the aqueous phase solution is prepared by the steps of:
the hyperbranched polyamide additive and the polyamine of the example 3 are added into deionized water with the temperature of 40 ℃ and the surfactant, and stirred for 0.5h, wherein the mass fraction of the hyperbranched polyamide additive is 1.5%, the mass fraction of the polyamine is 4%, and the mass fraction of the surfactant is 0.2%.
Wherein the oil phase solution is prepared by the following steps:
and adding phthaloyl chloride into n-hexane, and stirring at 55 ℃ for 1.5 h.
The polyamine is hexamethylenediamine, piperazine and m-phenylenediamine according to the mass ratio of 1:1:1, wherein the surfactant is sodium dodecyl benzene sulfonate.
Comparative example 2
Compared with example 5, the hyperbranched polyamide additive in example 5 was replaced by the material in comparative example 1, the remaining raw materials and the preparation process being unchanged.
Comparative example 3
Compared with example 5, the hyperbranched polyamide additive in example 5 is replaced by amino-terminated hyperbranched polyamide sold by Shanghai Jia Deer chemical technology Co., ltd, and the rest raw materials and the preparation process are unchanged.
The reverse osmosis membranes obtained in examples 5 to 7 and comparative example 2 were subjected to performance tests, the test items being as follows:
initial water flux test: loading each group of reverse osmosis membranes into a membrane pool, pre-pressing for 0.5h under 1.2MPa, and testing the water permeability in 1h under the pressure of 1.55MPa and the temperature of 25 ℃;
(II) salt cutting rate test: loading each group of reverse osmosis membranes into a membrane pool, pre-pressing for 0.5h under 1.2MPa, and testing the change of the mass concentration of the sodium chloride in the sodium chloride raw water solution and the permeate solution with the initial mass concentration of 2mg/mL in 1h under the pressure of 1.55MPa and the temperature of 25 ℃;
(III) contamination resistance: loading the reverse osmosis membrane into a cross-flow membrane pool, and operating for 2 hours under 1.55MPa by taking 2mg/mL NaCl aqueous solution as a circulating medium to obtain stable water flux (F0); then adding pollutant BSA into the circulating liquid to enable the mass concentration of the pollutant BSA to reach 1mg/mL, and continuously operating for 12 hours; flushing the reverse osmosis membrane with deionized water at a flow rate of 5.2L/min for 2h after discharging the polluted liquid, and discharging liquid; finally, under the same pressure, the reverse osmosis membrane is operated for 2 hours by taking 2mg/mL NaCl aqueous solution as a circulating medium, the water flux (Ft) of the reverse osmosis membrane is tested, and the water Flux Recovery Rate (FRR) is calculated by the following formula: frr=ft/f0×100%;
the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, compared with comparative examples 2 and 3, the reverse osmosis membranes prepared in examples 5 to 7 are more excellent in reverse osmosis performance, have a pressure of 1.55MPa, have a raw water concentration (NaCl) of 2mg/mL, a temperature of 25 ℃, have a recovery rate of water flux of more than 96.5% after 12 hours of pollution under the condition that bovine serum albumin is 1mg/mL, have a water flux of more than 46.3L/m2.h, and have a salt interception rate of more than 99.6%, which indicates that the reverse osmosis membrane prepared in the invention has higher water flux and salt interception rate and excellent pollution resistance.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The preparation method of the reverse osmosis membrane is characterized by comprising the following steps of:
firstly, adding hyperbranched polyamide additive and polyamine into deionized water containing surfactant and at 20-40 ℃ and stirring for 0.5-1.5h to obtain aqueous phase solution;
secondly, adding aromatic acyl chloride into an organic solvent, and stirring for 1-1.5h at 35-55 ℃ to obtain an oil phase solution;
thirdly, soaking the polysulfone support membrane in the aqueous phase solution for 1-5min, taking out, pressing to remove surface liquid, drying in the shade at room temperature to obtain a semi-finished product, pouring the oil phase solution into the surface of the semi-finished product, standing for 10s, pouring the oil phase solution out, and obtaining the reverse osmosis membrane after the surface organic solvent is completely volatilized;
the hyperbranched polyamide additive is prepared by the following steps:
dropwise adding tri (2-aminoethyl) amine into vanillin methyl ester monomer, heating to 100 ℃ after dropwise adding, starting stirring, dropwise adding N, N-dimethylacetamide after reacting for 2 hours, reacting for 2 hours at 120 ℃ after dropwise adding, and reacting for 6-7 hours at 140 ℃ to obtain amino-terminated hyperbranched polyamide;
adding the amino-terminated hyperbranched polyamide into methanol, adding a betaine type amphoteric ion compound containing carbon-carbon double bonds, and continuously stirring at room temperature for reacting for 48 hours to obtain a hyperbranched polyamide additive;
the ratio of vanillin methyl ester monomer, tri (2-aminoethyl) amine and N, N-dimethylacetamide is 1g:0.59-0.67g:4mL;
the dosage of the betaine type amphoteric ion compound containing carbon-carbon double bonds is 2-3% of the mass of the amino-terminated hyperbranched polyamide;
the betaine type amphoteric ion compound containing carbon-carbon double bond is one or more of N, N-dimethyl (methacryloxyethyl) ammonium propane sulfonic acid inner salt, N-dimethyl-N-methacrylamidopropyl-N, N-dimethyl-N-propane sulfonic acid inner salt, N-dimethyl-N-acrylamidopropyl-N-propane sulfonic acid inner salt and N, N-dimethyl-N-acrylamidopropyl-N-propane sulfonic acid inner salt;
the preparation steps of the vanillin methyl ester monomer are as follows:
dissolving vanillin in absolute ethyl alcohol, stirring and heating to 70 ℃, dropwise adding an absolute ethyl alcohol solution of p-phenylenediamine, and carrying out heat preservation and stirring reaction for 2 hours after the dropwise adding is finished to obtain an amino-terminated vanillin Schiff base compound;
mixing methanol, an amino-terminated vanillin Schiff base compound and methyl acrylate, and heating to reflux for 5-7h under the protection of nitrogen to obtain a vanillin methyl ester monomer;
the molar ratio of vanillin to p-phenylenediamine is 1:1, the mass ratio of the amino-terminated vanillin Schiff base compound to the methyl acrylate is 2.6:2.5-3.2.
2. The method for preparing a reverse osmosis membrane according to claim 1, wherein the mass fraction of the hyperbranched polyamide additive in the aqueous phase solution is 1-1.5%.
3. The method for preparing a reverse osmosis membrane according to claim 1, wherein the mass fraction of polyamine in the aqueous phase solution is 2-4% and the mass fraction of surfactant is 0.1-0.8%.
4. A reverse osmosis membrane prepared by the method of any one of claims 1-3.
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